DE1016387B - Process for the preparation of acetate rayon dyes - Google Patents

Description

GERMAN

It has been found that valuable acetate rayon dyes are particularly simple and convenient Way can be prepared if one mole of a mixture consisting of 1, 4-dioxyanthraquinone and a leuco compound of an anthraquinone which is in the 1- and 4-positions each through an oxy group or amino group is composed simultaneously with about 1 mole of an aliphatic Amine, ammonia can act and then optionally those present in the mixture obtained in this way Leuco compounds oxidized.

As leuco compounds of the specified type, for. B. those used in 1- and 4-position each by an oxy group or an amino group, in particular a primary or an alkylamino group, are substituted, so for example the leuco compound of 1, 4 - dioxyanthrachione, des 1, 4-diaminoanthraquinone, des l-oxy-4-aminoanthraquinone, the 1,4-di-alkylamino, l-amino-4-alkylamino or l-oxy-4-alkylaminoanthraquinones.

Among the aliphatic amines, the low molecular weight amines, ζ, are the main ones. B. those with 1 to 4 carbon atoms, give good results. These amines can optionally also contain oxy groups. In particular, primary amines can be used whose carbon chain can be straight or branched. Examples are: methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, /? - oxyethylamine, γ-oxypropylamine and β, -dioxypropylamine.

The ratio between the amount of 1,4-dioxyanthraquinone and the amount of leuco compound of the type specified can be used in the present process fluctuate within wide limits. Very good results are e.g. B. achieved if you add 4 parts of 1, 4-dioxyanthraquinone about 1 part of the leuco compound used. Of course you can also have more leuco connection use, for example, about the same amount of leuco compound as 1,4-dioxyanthraquinone; this however, in most cases it is not necessary and does not offer any advantages; an increased level of Leuco compound generally only causes an increased consumption of oxidizing agent the subsequent oxidation.

In the process according to the invention, 1 mole of the mixture of 1,4-dioxyanthraquinone is used and leuco compound about 1 mole of the amine and advantageously more than 1 mole, suitably about 2 to 3 moles of ammonia.

Instead of producing the leuco compound of 1,4-dioxyanthraquinone in a separate process, one can also use part of the 1,4-dioxyanthraquinone which is used in the process according to the invention

Method of manufacture
of acetate rayon dyes

Applicant:
CIBA Aktiengesellschaft, Basel (Switzerland)

Representative: Dipl.-Ing. E. Splanemann, patent attorney,
Hamburg 36, Neuer Wall 10

Claimed priority:
Switzerland from May 30, 1952 and April 2, 1953

Dr. Paul Großmann, Binningen (Switzerland),
has been named as the inventor

will, reduce in the reaction mixture itself to the leuco compound and then or during the Reduktionsvarganges or at the same time with this the reaction with ammonia and optionally the Alkylamine begin. Zinc dust or sodium hydrosulfide, for example, can be used as reducing agents Consideration.

The reactions of the present process are expediently carried out in an aqueous medium and advantageously in the presence of a water-soluble, organic solvent, such as. B. methanol or ethanol. she but can also be used in organic solvents, e.g. B. in water-soluble organic solvents in the absence of water or in the presence of small amounts of water or in water-insoluble organic Solvents such as toluene, xylene, can be carried out in the absence of water. One moderately increased reaction temperature, e.g. B. such from 60 to 120 °, generally ensures a smooth course of the reactions of the present proceedings.

The reaction with ammonia and an aliphatic amine is expediently carried out in a closed vessel carried out under pressure. It can be assumed that the oxy groups are the first in the leuco compound replaced by amino and alkyl amino groups or the amino groups by alkylamino groups will; the resulting substituted in the 1- and / or 4-position by amino or alkylamino groups Leuco compounds are then apparently able to reduce the 1,4-dioxyanthraquinone to the leuco compound, whereby they themselves are oxidized to the corresponding anthraquinones. Go this way

709 693/380

the two reactions, probably side by side, continue until practically all 1,4-dioxyanthraquinone is used up. Finally, a mixture of 1,4-diaminoanthraquinone and 1,4-dialkylaminoanthraquinone is obtained and l-amino-4-alkylaminoanthraquinone as well the leuco compounds of such substances.

Unless, for some reason, the presence of leuco compounds in the reaction mixture obtained is desired, or at least acceptable, or if not an oxidation of the leuco compounds during further processing by themselves to a sufficient extent takes place, the leuco compounds are after the reaction with the ammonia and the aliphatic amine to oxidize in a known manner, which is advantageous without intermediate deposition and, provided that The reaction mixture does not already contain one, is carried out with the addition of an organic solvent. Here you can use the usual oxidizing agents for such oxidations, such. B. alkali methanol with 36 parts of isopropylatin and 112.5 parts of 25% aqueous ammonia in a stirred autoclave Heated to 100 ° for 12 hours. The dye is then oxidized and isolated according to the instructions of Example 1. The dye thus obtained dyes acetate rayon in slightly more reddish tones than the dye according to the information in Example 1, first paragraph.

Example 3

80 parts of 1,4-dioxyanthraquinone and 25 parts Leuco-1,4-dioxyanthraquinone in 400 parts of methanol with 36.2 parts of isopropylamine and 112.5 parts 25% aqueous ammonia in a stirred autoclave first 5 hours at 60 ° and then 12 hours heated to 100 °. The dye is then oxidized and isolated as described in Example 1. The dye obtained in this way dyes acetate silk in shades with a slightly more reddish cast than that according to the information

chlorate or air, with the addition of copper acetate 20 from Example 1, first paragraph, available dye.

and / or use piperidine. Particularly beneficial

is 3-nitrobenzene-1-sulfonic acid, which is appropriate Example 4

80 parts of 1,4-dioxyanthraquinone and 25 parts Leuko-1, 4-dioxyanthraquinone are in 400 parts

is used in the form of an alkali salt.

The according to the method according to the invention

Halthchen products represent .wertrolle, partly new _a5 methanol with 16 parts of methylamine and 112.5 parts of dyes, which can be used to color various ₂ 5% aqueous ammonia in the autoclave S Stun materials. They are suitable for _{the a} * _{f 6 (} p _{and then} heated to 100 ° for 12 hours.

The dye is then oxidized and isolated as in Example 1. It significantly dyes acetate rayon

mainly used for dyeing cellulose esters, such as acetate rayon or cellulose acetate films, as well

synthetic fibers, ζ. B. _bluish from such Superpoly- 30 _vio i _e tablets than the tones in accordance with the

amides or super-polyurethanes. The dyes _{first paragraph of} Example 1 available dye.

_S1 are _{generally similar} in this use

due to its particularly good abundance. Given-

_{if necessary, they} can be used according to the present process or in.

products also available as intermediates 35 ^J

to serve.

Place of methylamine ethylamine, n-propylamine

Example 5 of German Patent 736 901 shows the preparation of l-amino-4-isopropylatninoanthraquinone by implementing a mixture

Example 5

The procedure is as in Example 4, first paragraph, but using only 10 parts of methyl instead of 16 parts

In the following examples, unless stated otherwise, the parts are parts by weight and the percentages are percentages by weight.

example 1

80 parts of 1,4-dioxyanthraquinone and 25 parts of leuco-1,4-dioxyanthraquinone are in 400 parts Methanol with 30.5 parts of ^ -oxyethylamine and 90 parts

of 1,4-dioxyanthrachiiion and leuco-1,4-diamino-40 amine and thus receives a dye, the acetate art

Anthraquinone with isopropylamine and subsequent oxy-silk colors in shades similar to the one according to

dation described. Compared to this method, Example 1, first paragraph, available dye,

However, if the present process has the advantage. Similar dyes are obtained if instead of

on, not only to be simpler and therefore cheaper, 10 parts methylamine, 15 parts ethylamine, 20 parts

but also for dyes with greater abundance- 45 n-propylamine or 25 parts n-butylamine used, ability to lead.

Eg 1 6

160 parts of 1,4-dioxyanthraquinone and 50 parts of leuco-1,4-dioxyanthraquinone are in 800 parts Methanol with 75 parts of sec-butylamine and 225 parts of 25% strength methyl alcoholic ammonia solution in Autoclave heated to 60 ° for 5 hours and then to 100 ° for 12 hours. It is oxidized and isolated accordingly the procedure given in Example 1.

len 25% aqueous ammonia in a stirred autoclave 55 The dye dyes acetate rayon in very similar

first for 5 hours at 60 ° and then 12 hours i _ic h _{s tones as} that of the example. 3

heated to 100 ° for a long time. A solution of 10.5 parts of 3-nitrobenzene-1-sulfonic acid sodium is then added in 50 parts of water and keep the whole thing for a further 4 hours at 100 °. After cooling, it is filtered and the residue washed with water. The dye obtained in this way dyes by the usual dispersion method Acetate rayon in very strong

blue-violet tones. .,,, -r.

Instead of yS-oxyethylamine, y-oxypropyl-65 ^{silk can also be used somewhat bluer than} that of Example 3.

use amine or ß, v-dipxypropylamine. -n · 1 0

Example 0

e 1 s ρ 1 e -y- _{an procedure} according to the information in example 7,

80 parts of 1,4-dioxyanthraquinone and 25 parts replaces 27.5 parts of leuko-l-oxy-4-isopropylamino ¹

Leuco-1,4-diaminoanthraquinone becomes in 400 parts 70 anthraquinone through 27.5 parts leuco-1-amino-4-isof

Example 7

The procedure described in Example 3 is followed, but 25 parts of leuco-1,4-dioxyanthraquinone are replaced by 27.5 parts of leuco-1-oxy-4-isopropylaminoanthraquinone and 36.2 parts isopropylamine by 27 parts isopropylamine. This dye stains acetate art

propylaminoanthraquinone. This dye stains Acetate rayon somewhat more reddish than that of Example 3.

Example 19

The procedure described in Example 7 is followed, but 27.5 parts of leuco-1-oxy-4-isopropylaminoanthraquinone are replaced by 27.5 parts of leuco-1, 4-di - (/? - oxyäthylamino) -anthraquinone. This dye dyes acetate rayon in shades similar to the one of example 3.

Example 10

The procedure is as in Example 3, but oxidizes with 3.5 parts of sodium chlorate instead of with 10.5 parts of 3-nitrobenzene-1-sulfonic acid sodium. This dye dyes acetate rayon in shades very similar to that of Example 3.

Example 11 _ao

160 ¹ part of 1,4-dioxyanthraquinone and 50 parts of leuco-1,4-dioxyanthraquinone are heated in 860 parts of 8% solution of ammonia gas in isobutyl alcohol with 72 parts of isopropylamine in an autoclave at 100 ° for 12 hours. 10 parts of nitrobenzene are added and the mixture is heated to 100 ° for a further 4 hours. The dye is isolated by evaporation. The coloration on acetate rayon is very similar to that of the dye according to Example 3.

30 Example 12

The procedure is as in Example 11, but oxidizes by passing in air for an hour at 95 to 100 ° with the addition of 1 part of copper acetate and 3 parts of piperidine. One isolates the dye, as indicated in Example 11. The coloration on acetate rayon is similar to that of the dye Example 11 very similar.

Example 13

4.0

80 parts of 1,4-dioxyanthraquinone and 25 parts of leuco-1,4-dioxyanthraquinone are in an autoclave 36 parts of isopropylamine are added in 500 parts of xylene. Then you press the closed one Autoclave 29 parts of ammonia gas and heated to 100 to 110 ° for 12 hours. 5 parts of nitrobenzene are added added and heated to 100 ° for a further 4 hours. The dye is isolated by evaporation or by steam distillation. It dyes acetate artificial silk in shades more reddish than that of the example 11.

Example 14

105 parts of 1,4-dioxyanthraquinone are heated in 400 parts of methanol with 16 parts of methylamine, 112.5 parts of 25% strength aqueous ammonia and 23 parts of 85% strength sodium hydrosulfite in an autoclave at 100 ° for 12 hours. The dye is oxidized and isolated as in Example 1. It dyes acetate rayon _g in shades similar to the dye according to Example 4.

Example 15

The procedure is as in Example 14, but the 23 parts of sodium hydrosulfite are replaced by 8 parts of zinc dust. (90%) and receives a very similar dye.

Example 16

The procedure is as in Example 15, but a further 20 parts of sodium bicarbonate are added, creating a something more extensive. Dye received as according to example 15th

B e i s ρ i e 1 17

80 parts of 1,4-dioxyanthraquinone and 25 parts of leuco-1,4-dioxyanthraquinone are in 250 parts of methanol with 36 parts of isopropylamine and 215 parts of 17.7% methyl alcoholic ammonia in one Stirring autoclave heated to 100 ° for 12 hours. 10.5 parts of 3-nitrobenzene-1-sulfonic acid sodium are added added and heated to 100 ° for 4 hours. It is filtered cold and washed with a little methanol and water. The dye obtained dyes acetate rayon in very strong and genuine blue-violet Tones.

Example 18

160 parts of 1,4-dioxyanthraquinone and 50 parts of leuco-1,4-dioxyanthraquinone are in 800 parts Water with 270 parts of 25% aqueous ammonia and 61 parts of oxyethylamine in a stirred autoclave Heated to 100 ° for 12 hours. After cooling, it is filtered, washed with water and dried. After suitable pasting, the dye dyes acetate artificial silk in strong, blue-violet tones.

The reaction proceeds in a similar way if the 61 parts / 5-oxyethylamine is replaced by 32 parts of methylamine replaced.

Example 19

160 parts of 1,4-dioxyanthraquinone and 50 parts Leuco-1,4-dioxyanthraquinone are dissolved in 800 parts of water with 270 parts of 25% aqueous ammonia and 60 parts of isopropylamine heated to 100 ° in a stirred autoclave for 12 hours. After cooling down is filtered and washed with water. The product obtained is then heated in 750 parts of methyl alcohol with 250 parts of ammonia and 20 parts of 3-nitrobenzene-1-sulfonic acid sodium for 4 hours 100 °, filtered cold and washed with water. The resulting dye stains acetate rayon in vivid colors and real blue-violet tones.

Claims (6)

PATENT CLAIMS: 1. A process for the preparation of acetate artificial silk dyes, characterized in that one to 1 mole of a mixture consisting of 1,4-dioxyanthraquinone and a leuco compound an anthraquinone divided into 1- and 4-S by a hydroxyl or amino group is substituted, composed simultaneously with about 1 mole of an aliphatic amine, ammonia allowed to act and, if appropriate, the leuco compound present in the mixture thus obtained oxidized. 2. The method according to claim 1, characterized in that one mole of the out 1, 4-dioxyanthraquinone and leuco compound composing mixture more than 1 mol, preferably about 2 to 3 moles of ammonia are used. 3. The method according to any one of claims 1 and 2, characterized in that the quantitative ratio of 1,4-dioxyanthraquinone to leuco compound at least 1: 1 and preferably is about 4: 1. 4. The method according to any one of claims 1 to 3, characterized in that the leuco compound generated in the reaction mixture itself by adding a reducing agent. 7 8 5. The method according to one of claims 1 to 3, co-compound of the 1, 4-diaminoanthraquinone through this marked by turning the leuco. compound of 1,4-dioxyanthraquinone turns. Considered publications: 6. The method according to any one of claims 1 5 German Patent No. 716 046; to 3, characterized in that the Leu USA. Patents Nos. 2,228,884, 2,335,680. © 709,698 / 380 9 ·. 57